DUT-5

Crystal structure of DUT-5. Perspective view of the pore cross section.

Crystal structure of DUT-5. Orthographic view of the M-OH chains.

DUT-5 (DUT represents English D resden U niversity of T echnology ) the name of a material which is to the substance class of metal-organic frameworks (engl. Metal-organic framework , MOF) counts. The framework structure is an expanded version of the MIL-53 structure and consists of aluminum ions (Al ³⁺ ) as metal centers and biphenyl-4,4'-dicarboxylate (BPDC) as linker molecules . In the DUT-5 structure, inorganic [M-OH] zigzag chains (so-called secondary building units , SBUs) are connected to four adjacent inorganic chains by means of the biphenyl 4,4'-dicarboxylate linkers, creating one-dimensional , diamond-shaped pores arise.

Known structural analogues

The first DUT-5 structure produced was synthesized with Al ³⁺ as the metal center. Other metals with the oxidation numbers + II or + IV were later used instead of Al ³⁺ to produce materials with DUT-5-analogous structures.

Overview of unfunctionalized DUT-5 analogs
Surname	Metal center and Oxidation number	Year of Initial release
DUT-5 (Al)	Al ³⁺	2009
COMOC-2	V ³⁺ / V ⁴⁺ , V ⁴⁺	2013
Mg (4S-PNO) (BPDC)	Mg ²⁺	2018
Co (4S-PNO) (BPDC)	Co ²⁺	2018

Due to the modular structure of metal-organic framework compounds, other organic molecules can be used as linkers instead of biphenyl-4,4'-dicarboxylate if they are structurally similar to biphenyl-4,4'-dicarboxylate. For the development of functionalized DUT-5 materials, functional biphenyl-4,4'-dicarboxylates were used, which have additional functional groups on the benzene rings. These functional groups in the pores of the DUT-5 framework were used on the one hand for post-synthetic modifications and on the other hand for changing adsorption properties.

Overview of functionalized DUT-5 analogs
Functional linker	Metal center
Functional linker	Al	V	Ga
2,2'-bipyridine-5,5'-dicarboxylate	MOF-253	-	COMOC-4
4,4'-Bibenzoic acid-2,2'-sulfone			-
2-amino- [1,1 '] - biphenyl-4,4'-dicarboxylate		-	-
2-ethynyl [1,1 '] biphenyl-4,4'-dicarboxylate		-	-
2-azido [1,1 '] - biphenyl-4,4'-dicarboxylate		-	-
2-nitro- [1,1 '] - biphenyl-4,4'-dicarboxylate		-	-
2-iodo [1,1 '] biphenyl-4,4'-dicarboxylate		-	-

Individual evidence

↑ ^a ^b ^c Irena Senkovska, Frank Hoffmann, Michael Fröba, Juergen Getzschmann, Winfried Böhlmann: New highly porous aluminum based metal-organic frameworks: Al (OH) (ndc) (ndc = 2,6-naphthalene dicarboxylate) and Al (OH ) (bpdc) (bpdc = 4,4′-biphenyl dicarboxylate) . In: Microporous and Mesoporous Materials . tape 122 , no. 1-3 , June 2009, pp. 93-98 , doi : 10.1016 / j.micromeso.2009.02.020 .
↑ Franck Millange, Richard I. Walton: MIL-53 and Its Analogues Isoreticular: a Review of the Chemistry and Structure of a prototypical Flexible Metal-Organic Framework . In: Israel Journal of Chemistry . tape 58 , no. 9-10 , October 2018, pp. 1019-1035 , doi : 10.1002 / ijch.201800084 .
^ Ying-Ya Liu, Sarah Couck, Matthias Vandichel, Maciej Grzywa, Karen Leus: New V IV -Based Metal-Organic Framework Having Framework Flexibility and High CO 2 Adsorption Capacity . In: Inorganic Chemistry . tape 52 , no. 1 , January 7, 2013, ISSN 0020-1669 , p. 113-120 , doi : 10.1021 / ic301338a .
^ ^A ^b Hannah Kunicki, Thomas W. Chamberlain, Guy J. Clarkson, Reza J. Kashtiban, Joseph E. Hooper: An expanded MIL-53-type coordination polymer with a reactive pendant ligand . In: CrystEngComm . tape 20 , no. 31 , 2018, ISSN 1466-8033 , p. 4355-4358 , doi : 10.1039 / C8CE00891D .
↑ Ceylan Yildiz, Ksenia Kutonova, Simon Oßwald, Alba Titze ‐ Alonso, Johannes Bitzer: Post ‐ synthetic Modification of DUT ‐ 5 ‐ based Metal Organic Frameworks for the Generation of Single ‐ site Catalysts and their Application in Selective Epoxidation Reactions . In: ChemCatChem . tape 12 , no. 4 , February 20, 2020, ISSN 1867-3880 , p. 1134-1142 , doi : 10.1002 / cctc.201901434 .
^ ^A ^b Eric D. Bloch, David Britt, Chain Lee, Christian J. Doonan, Fernando J. Uribe-Romo: Metal Insertion in a Microporous Metal - Organic Framework Lined with 2,2′-Bipyridine . In: Journal of the American Chemical Society . tape 132 , no. 41 , October 20, 2010, ISSN 0002-7863 , p. 14382–14384 , doi : 10.1021 / ja106935d .
↑ ^a ^b Ying-Ya Liu, Roel Decadt, Thomas Bogaerts, Karen Hemelsoet, Anna M. Kaczmarek: Bipyridine-Based Nanosized Metal – Organic Framework with Tunable Luminescence by a Postmodification with Eu (III): An Experimental and Theoretical Study . In: Journal of Physical Chemistry C . tape 117 , no. 21 , May 30, 2013, ISSN 1932-7447 , p. 11302-11310 , doi : 10.1021 / jp402154q .
↑ ^a ^b Guangbo Wang, Karen Leus, Sarah Couck, Pieter Tack, Hannes Depauw: Enhanced gas sorption and breathing properties of the new sulfone functionalized Comoc-2 metal organic framework . In: Dalton Transactions . tape 45 , no. 23 , 2016, ISSN 1477-9226 , p. 9485-9491 , doi : 10.1039 / C6DT01355D .
↑ Sarah Couck, Ying-Ya Liu, Karen Leus, Gino V. Baron, Pascal Van der Voort: gas phase adsorption of alkanes, alkenes and aromatics on the sulfone-DUT 5 metal organic framework . In: Microporous and Mesoporous Materials . tape 206 , April 2015, p. 217–225 , doi : 10.1016 / j.micromeso.2014.11.028 .
↑ ^a ^b ^c Selda Halis, Nele Reimer, Arne Klinkebiel, Ulrich Lüning, Norbert Stock: Four new Al-based microporous metal-organic framework compounds with MIL-53-type structure containing functionalized extended linker molecules . In: Microporous and Mesoporous Materials . tape 216 , November 2015, p. 13-19 , doi : 10.1016 / j.micromeso.2015.01.030 .
↑ ^a ^b ^c ^d Meike A. Gotthardt, Sylvain Grosjean, Tobias S. Brunner, Johannes Kotzel, Andreas M. Gänzler: Synthesis and post-synthetic modification of amine-, alkyne-, azide- and nitro-functionalized metal – organic frameworks based on DUT-5 . In: Dalton Transactions . tape 44 , no. 38 , 2015, ISSN 1477-9226 , p. 16802-16809 , doi : 10.1039 / C5DT02276B .
↑ Babak Tahmouresilerd, Michael Moody, Louis Agogo, Anthony F. Cozzolino: The impact of an isoreticular expansion strategy on the performance of iodine catalysts supported in multivariate zirconium and aluminum metal – organic frameworks . In: Dalton Transactions . tape 48 , no. 19 , 2019, ISSN 1477-9226 , p. 6445-6454 , doi : 10.1039 / C9DT00368A .

[:0-1] Irena Senkovska, Frank Hoffmann, Michael Fröba, Juergen Getzschmann, Winfried Böhlmann: New highly porous aluminum based metal-organic frameworks: Al (OH) (ndc) (ndc = 2,6-naphthalene dicarboxylate) and Al (OH ) (bpdc) (bpdc = 4,4′-biphenyl dicarboxylate) . In: Microporous and Mesoporous Materials . tape 122 , no. 1-3 , June 2009, pp. 93-98 , doi : 10.1016 / j.micromeso.2009.02.020 .

[2] Franck Millange, Richard I. Walton: MIL-53 and Its Analogues Isoreticular: a Review of the Chemistry and Structure of a prototypical Flexible Metal-Organic Framework . In: Israel Journal of Chemistry . tape 58 , no. 9-10 , October 2018, pp. 1019-1035 , doi : 10.1002 / ijch.201800084 .

[3] Ying-Ya Liu, Sarah Couck, Matthias Vandichel, Maciej Grzywa, Karen Leus: New V IV -Based Metal-Organic Framework Having Framework Flexibility and High CO 2 Adsorption Capacity . In: Inorganic Chemistry . tape 52 , no. 1 , January 7, 2013, ISSN 0020-1669 , p. 113-120 , doi : 10.1021 / ic301338a .

[:1-4] A ^b Hannah Kunicki, Thomas W. Chamberlain, Guy J. Clarkson, Reza J. Kashtiban, Joseph E. Hooper: An expanded MIL-53-type coordination polymer with a reactive pendant ligand . In: CrystEngComm . tape 20 , no. 31 , 2018, ISSN 1466-8033 , p. 4355-4358 , doi : 10.1039 / C8CE00891D .

[5] Ceylan Yildiz, Ksenia Kutonova, Simon Oßwald, Alba Titze ‐ Alonso, Johannes Bitzer: Post ‐ synthetic Modification of DUT ‐ 5 ‐ based Metal Organic Frameworks for the Generation of Single ‐ site Catalysts and their Application in Selective Epoxidation Reactions . In: ChemCatChem . tape 12 , no. 4 , February 20, 2020, ISSN 1867-3880 , p. 1134-1142 , doi : 10.1002 / cctc.201901434 .

[:4-6] A ^b Eric D. Bloch, David Britt, Chain Lee, Christian J. Doonan, Fernando J. Uribe-Romo: Metal Insertion in a Microporous Metal - Organic Framework Lined with 2,2′-Bipyridine . In: Journal of the American Chemical Society . tape 132 , no. 41 , October 20, 2010, ISSN 0002-7863 , p. 14382–14384 , doi : 10.1021 / ja106935d .

[:5-7] Ying-Ya Liu, Roel Decadt, Thomas Bogaerts, Karen Hemelsoet, Anna M. Kaczmarek: Bipyridine-Based Nanosized Metal – Organic Framework with Tunable Luminescence by a Postmodification with Eu (III): An Experimental and Theoretical Study . In: Journal of Physical Chemistry C . tape 117 , no. 21 , May 30, 2013, ISSN 1932-7447 , p. 11302-11310 , doi : 10.1021 / jp402154q .

[:6-8] Guangbo Wang, Karen Leus, Sarah Couck, Pieter Tack, Hannes Depauw: Enhanced gas sorption and breathing properties of the new sulfone functionalized Comoc-2 metal organic framework . In: Dalton Transactions . tape 45 , no. 23 , 2016, ISSN 1477-9226 , p. 9485-9491 , doi : 10.1039 / C6DT01355D .

[9] Sarah Couck, Ying-Ya Liu, Karen Leus, Gino V. Baron, Pascal Van der Voort: gas phase adsorption of alkanes, alkenes and aromatics on the sulfone-DUT 5 metal organic framework . In: Microporous and Mesoporous Materials . tape 206 , April 2015, p. 217–225 , doi : 10.1016 / j.micromeso.2014.11.028 .

[:2-10] Selda Halis, Nele Reimer, Arne Klinkebiel, Ulrich Lüning, Norbert Stock: Four new Al-based microporous metal-organic framework compounds with MIL-53-type structure containing functionalized extended linker molecules . In: Microporous and Mesoporous Materials . tape 216 , November 2015, p. 13-19 , doi : 10.1016 / j.micromeso.2015.01.030 .

[:3-11] Meike A. Gotthardt, Sylvain Grosjean, Tobias S. Brunner, Johannes Kotzel, Andreas M. Gänzler: Synthesis and post-synthetic modification of amine-, alkyne-, azide- and nitro-functionalized metal – organic frameworks based on DUT-5 . In: Dalton Transactions . tape 44 , no. 38 , 2015, ISSN 1477-9226 , p. 16802-16809 , doi : 10.1039 / C5DT02276B .

[12] Babak Tahmouresilerd, Michael Moody, Louis Agogo, Anthony F. Cozzolino: The impact of an isoreticular expansion strategy on the performance of iodine catalysts supported in multivariate zirconium and aluminum metal – organic frameworks . In: Dalton Transactions . tape 48 , no. 19 , 2019, ISSN 1477-9226 , p. 6445-6454 , doi : 10.1039 / C9DT00368A .